Abstract
Reaction of the potassium salt of N‐(diisopropoxyphosphoryl)thiobenzamide (__i__PrO)~2~P(O)NHC(S)C~6~H~5~ (HL) with Zn^II^ and Cd^II^ cations in aqueous EtOH leads to three different complexes: [Zn(L‐O,S)~2~] (1), [Cd~2~(L‐O,S)~4~] (2) and [Cd(HL‐O)~2~(L‐O,S)~2~] (3). The structures of these compounds were investigated by single‐crystal X‐ray diffraction analysis, EI‐MS and ES‐MS, IR, ^1^H, ^13^C and ^31^P NMR spectroscopy and microanalysis. The zinc(II) atom in complex 1 is in a distorted tetrahedral ZnO~2~S~2~ environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. The cadmium(II) complex 2 is centrosymmetric and consists of dimeric species. Two [Cd(L‐O,S)~2~] moieties are connected by two bridging [S–Cd–S] units through the sulfur atoms of the ligand C=S groups. Complex 2 has a distorted trigonal‐bipyramidal Cd(O^ax^)~2~(S^eq^)~3~ core. Complex 3 has a tetragonal‐bipyramidal environment, Cd(O^ax^)~2~(O^eq^)~2~(S^eq^)~2~, and two neutral ligand molecules are coordinated in the axial positions through the oxygen atoms of the P=O groups. The base of the bipyramid is formed by two anionic ligands in a typical 1,5‐O,S coordination mode. The ligands are in a trans configuration. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)